Composition of epoxy resin and reactive vinyl polymer produced by living radical polymerization

ABSTRACT

A composition comprises (A) an exopy resin and (B) a vinyl polymer having a reactive functional group selected from the group consisting of an alcoholic hydroxyl, phenolic hydroxyl, amino, amido and carboxyl group prepared by living radical polymerization, particularly the atom transfer radical polymerization of a vinyl polymer having a halogen atom and conversion of the halogen atom to a reactive functional group.

TECHNICAL FIELD

The present invention relates to an epoxy resin composition. Moreparticularly, it relates to an epoxy-terminated vinyl polymer, acomposition comprising the polymer and a flexible composition comprisingan epoxy resin and a reactive functional group-containing vinyl polymer.

BACKGROUND ART

When combined with a curing agent, epoxy resins give cured productshaving a three-dimensionally crosslinked structure and thus exhibitingvarious desirable characteristics. Crosslinked epoxy groups areexploited in a wide range of applications, such as paints,electrics/electronics, civil engineering/building, adhesives, andcomposite materials, owing to excellence in the balance between heatresistance and mechanical/physical properties and in electricalcharacteristics adhesive characteristics and corrosion resistance, amongothers, and to the ease of molding.

On the other hand, epoxy resins are generally hard and brittle by natureand may form cracks upon exposure to stress strain or thermal shock onthe occasion of curing or in use, hence epoxy resins are required to berendered tenacious and flexible. In the field of IC sealing, forinstance, where packages are becoming smaller and thinner, improvementin crack resistance is needed.

As a means for providing epoxy resins with flexibility, there maybementioned the combined use of a flexible epoxy resin. The flexible epoxyresin includes, among others, diglycidyl esters of long-chain fattyacids such as linoleic acid dimer; polyglycidyl ethers of polyhydricalcohols such as glycerol, pentaerythritol and trimethylolpropane;diglycidyl ethers of polyalkylene glycols such as polyethylene glycol;and the like. However, long-chain fatty acid glycidyl esters are shortof alkali resistance and gasoline resistance, although they areexcellent in flexibility. Polyalkylene glycol glycidyl ethers also haveproblems, for example they are inferior in weathering resistance.

It is known that crosslinking functional group-terminated liquidoligomers, when used alone or combined with an appropriate curing agent,give cured products excellent in rubber elasticity. Thus, it is expectedthat an epoxy-terminated vinyl polymer, if successfully obtained in asimple and easy manner, might serve as a novel flexible epoxy resinexcellent in flexibility. Further, vinyl polymers show variouscharacteristics depending on the main chain skeleton thereof and,therefore, are amenable to molecular design according to the use/purposethereof.

As for the production of epoxy-terminated vinyl polymers, U.S.Pat. No.4,429,099, for instance, discloses a method which comprises reacting thetermini of polyisobutylene with a phenol in the manner of Friedel-Craftsreaction and further utilizing the reactivity of the phenol group tosynthesize an epoxy-terminated polyisobutylene. However, low-polaritypolymers such as polyisobutylene are poor in compatibility with epoxyresins and, if well dispersed, give a high viscosity.

In view of the above state of the art, it is an object of the presentinvention to provide a vinyl polymer with an epoxy group terminallyintroduced therein and an epoxy resin composition in which such polymeris used.

A further object of the invention is to provide an epoxy resincomposition having flexibility by adding a vinyl polymer having aterminal reactive functional group to an epoxy resin.

SUMMARY OF THE INVENTION

Thus, according to a first aspect thereof, the invention provides anepoxy resin composition

which comprises a vinyl polymer having a group represented by thefollowing general formula (1) at a main chain terminus

as well as a vinyl polymer having a group represented by the followinggeneral formula (1) at a main chain terminus.

In the above formula, R¹, R² and R³ are the same or different and eachrepresents a hydrogen atom, a monovalent hydrocarbon group containing 1to 10 carbon atoms or a monovalent group containing 1 to 10 carbon atomsas derived from two hydrocarbon groups by being bound together via anether bond or ester bond, and R¹ and R² or R² and R³may be combinedtogether at respective other termini to form a cyclic structure.

In accordance with a second aspect, the invention provides an epoxyresin composition

which comprises (A) an epoxy resin and (B) a vinyl polymer having a mainchain produced by living radical polymerization and a reactivefunctional group at a main chain terminus.

In the following, the present invention is described in detail.

DETAILED DISCLOSURE OF THE INVENTION

The first aspect of the invention lies in an epoxy resin compositioncomprising a vinyl polymer terminally having a group represented by thegeneral formula (1) shown above, namely an epoxy-terminated vinylpolymer.

In the general formula (1), R¹, R² and R³ are the same or different andeach represents a hydrogen atom, a monovalent hydrocarbon groupcontaining 1 to 10 carbon atoms or a monovalent group containing 1 to 10carbon atoms as derived from two hydrocarbon groups by being boundtogether via an ether bond or ester bond, and R¹ and R² or R²and R³ maybe combined together at respective other termini to form a cyclicstructure.

The monomer constituting the main chain of the above vinyl polymer isnot particularly restricted but maybe any of various monomers. Asexamples, there may be mentioned (meth)acrylic monomers such as(meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate,n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl(meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate,n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl(meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate,dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate,benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate,2-aminoethyl (meth)acrylate, γ-(methacryloyloxypropyl)trimethoxysilane,(meth)acrylic acid-ethylene oxide adducts, trifluoromethylmethyl(meth)acrylate, 2-trifluoromethylethyl (meth)acrylate,2-perfluoroethylethyl (meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl(meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl(meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate,2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl(meth)acrylate and 2-perfluorohexadecylethyl (meth)acrylate; styrenicmonomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene,and styrenesulfonic acid and salts thereof; fluorine-containing vinylmonomers such as perfluoroethylene, perfluoropropylene and vinylidenefluoride; silicon-containing vinyl monomers such asvinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleicacid and monoalkyl esters and dialkyl esters of maleic acid; fumaricacid and monoalkyl esters and dialkyl esters of fumaric acid; maleimidemonomers such as maleimide, methylmaleimide, ethylmaleimide,propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide,dodecylmaleimide, stearylmaleimide, phenylmaleimide andcyclohexylmaleimide; nitrile-containing vinyl monomers such asacrylonitrile and methacrylonitrile; amido-containing vinyl monomerssuch as acrylamide and methacrylamide; vinyl esters such as vinylacetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinylcinnamate; alkenes such as ethylene and propylene; conjugated dienessuch as butadiene and isoprene; vinyl chloride, vinylidene chloride,allyl chloride, allyl alcohol and so forth. These may be used singly ora plurality of them may be copolymerized. Preferred among them from theviewpoint of physical properties of products, among others, are styrenicmonomers and (meth)acrylic monomers, more preferably (meth)acrylic estermonomers, still more preferably acrylic ester monomers, and butylacrylate is most preferred. In the practice of the invention, thesepreferred monomers may be copolymerized with another monomer or othermonomers and, on that occasion, the content of these preferred monomersis preferably 40% by weight.

The molecular weight distribution of the above vinyl polymer is notparticularly restricted but the ratio (Mw/Mn) of weight averagemolecular weight (Mw) to number average molecular weight (Mn) asdetermined by gel permeation chromatography is generally less than 1.8,preferably not more than 1.7, more preferably not more than 1.6, stillmore preferably not more than 1.5, especially preferably not more than1.4, most preferably not more than 1.3. In GPC measurements in thepractice of the invention, the measurements are generally carried outusing polystyrene gel columns with chloroform as the mobile phase. Thenumber average molecular weight and so on can be determined on thepolystyrene equivalent basis.

The number average molecular weight of the above vinyl polymer is notparticularly restricted but preferably is within the range of 500 to1,000,000, more preferably 1,000to 100,000.

The vinyl polymer having a terminal structure represented by the generalformula (1) can be obtained by reacting the reactive functional group ofa reactive functional group-terminated vinyl polymer with a compoundrepresented by the general formula (2) given below. The reactivefunctional group is not particularly restricted but preferably is analcoholic hydroxyl group, a phenolic hydroxyl group, an amino group or acarboxyl group.

In the general formula (2), R¹, R² and R³ are as defined above. R⁴ andR⁵ are the same or different and each represents a hydrogen atom, amonovalent hydrocarbon group containing 1 to 10 carbon atoms or amonovalent group containing 1 to 10 carbon atoms as derived from twohydrocarbon groups by being bound together via an ether bond or esterbond. X represents a chlorine, bromine or iodine atom.

In the first aspect of the invention, the reactive functionalgroup-terminated vinyl polymer is produced by the following steps:

(1) Polymerizing a vinyl monomer(s) by the technique of living radicalpolymerization and

(2) Reacting, at the end point of the polymerization, the polymer with acompound having both a reactive function group and an ethylenicallyunsaturated group.

Thus, radical polymerization of a vinyl monomer(s) is carried out in themanner of living radical polymerization, typically atom transfer radicalpolymerization, followed by causing the species active inpolymerization, namely the polymer radical, to add to the ethylenicallyactive group of the compound having both ethylenically unsaturated groupand a reactive functional group as well, whereupon a reactive.functional group-terminated vinyl polymer can be obtained.

While “living polymerization”, in its narrow sense, means thepolymerization in which molecular chains grow while the terminalactivity thereof is always maintained, it generally includespseudo-living polymerization in which molecular chains grow whileterminally inactivated species and terminally active species are inequilibrium. It is the latter definition that applies in the presentinvention. In recent years, “living radical polymerization” has beenactively studied by a number of groups. As examples, there may bementioned, among others, the technique using such a radical cappingagent as a cobalt-porphyrin complex (J. Am. Chem. Soc., 1994, 116, 7943)or a nitroxide compound (Macromolecules, 1994, 27, 7228) and the atomtransfer radical polymerization (ATRP) technique using an organic halideor the like as an initiator and a transition metal complex as acatalyst. In spite of the fact that it belongs to the class of radicalpolymerization in which the rate of polymerization is high and atermination reaction such as mutual coupling of radicals readily occursand which is said to be difficult to control, living radicalpolymerization is hardly subject to such termination reaction and cangive a polymer with a narrow molecular weight distribution (Mw/Mn=1.1 to1.8) and renders it possible to control the molecular weight arbitrarilyby selecting the monomer/initiator charge ratio.

Further, “living radical polymerization” is characterized by nature inthat the structures of the polymer termini are distinct and terminalfunctional group introduction is easy and, therefore, it is preferred asthe method of producing a vinyl polymer terminally having a specificfunctional group. Among living radical polymerization techniques, theatom transfer radical polymerization technique is most preferred becauseof the ease of molecular weight and molecular weight distributioncontrol.

Atom transfer radical polymerization is characterized in that a vinylmonomer(s) is(are) polymerized using an organic halide (e.g. a compoundhaving a halogen atom at the α position, or a compound having a halogenatom at the benzyl position) or a halogenated sulfonyl compound as theinitiator and a transition metal complex as the catalyst.

The above organic halide or halogenated sulfonyl compound contains acarbon atom bound to a halogen atom and further bound to a carbonyl,phenyl or sulfonyl group, so that the carbon-halogen bond can be readilyactivated and can function as an initiator. Among typical examples ofsuch compound, there are the following: C₆H₅—CH₂X, C₆H₅—C(H)(X)CH₃,C₆H₅—C(X)(CH₃)₂ (where C₆H₅ represents a phenyl group and X represents achlorine, bromine or iodine atom); R⁸—C(H)(X)—CO₂R⁹, R⁸—C(CH₃)(X)—CO₂R⁹,R⁸—C(H)(X)—C(O)R⁹, R⁸—C(CH₃)(X)—C(O)R⁹ (where R⁸ and R⁹ are the same ordifferent and each represents a hydrogen atom, an alkyl group containing1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms oran aralkyl group containing 7 to 20 carbon atoms and X represents achlorine, bromine or iodine atom); R⁸-C₆H₄—SO₂X (where R⁸ represents ahydrogen atom, an alkyl group containing 1 to 20 carbon atoms, an arylgroup containing 6 to 20 carbon atoms or an aralkyl group containing 7to 20 carbon atoms and X represents a chlorine, bromine or iodine atom);and the like. By converting the terminal halogen of a polymer obtainedby using this initiator by the method mentioned later herein, a vinylpolymer having a group represented by the general formula (1) at oneterminus is produced.

An organic halide or halogenated sulfonyl compound having a functionalgroup other than the functional group serving to initiate thepolymerization may also be used. In that case, a polymer is producedwhich has the functional group bound to the initiator at one terminus ofthe main chain and the halogen group at the other terminus. As thefunctional group, there may be mentioned alkenyl, crosslinking silyl,hydroxyl, epoxy, amino, amido and carboxyl groups, among others. Whenthe terminal halogen atom of the polymer is converted to a substituenthaving a group of the general formula (1), a vinyl polymer having, atboth termini, functional groups which are the same or different. Bycoupling the terminal halogens together, it is possible to produce avinyl polymer which has functional groups at both termini.

The polymerization may also be carried out by using an organic halide orhalogenated sulfonyl compound having two or more initiation sites as theinitiator. In such case, a vinyl polymer having two or more halogengroups in each molecule is produced. When the termini of this polymerare converted by the method mentioned later herein, a vinyl polymerhaving two or more groups represented by the general formula (1) permolecule is obtained. By carrying out the polymerization using aninitiator having two initiation sites and converting the both termini ofthe polymer by the method mentioned later herein, a vinyl polymer havinga group of the general formula (1) at both termini is produced.

Specific examples of the initiator having two initiation sites are asfollows:

(In the above formulas, C₆H₄ represents a phenylene group, X representsa chlorine, bromine or iodine atom, R represents an alkyl groupcontaining 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbonatoms or an aralkyl group containing 7 to 20 carbon atoms and nrepresents an integer of 0 to 20);

(In the above formulas, X represents a chlorine, bromine or iodine atom,n represents an integer of 0 to 20 and C₆H₄ represents a phenylenegroup); and the like.

Living radical polymerization can be carried out in the absence of or inany of various organic solvents. As the solvents, there may be mentionedhydrocarbon solvents such as benzene and toluene; ether solvents such asdiethyl ether, tetrahydrofuran, diphenyl ether, anisole anddimethoxybenzene; halogenated hydrocarbon solvents such as methylenechloride, chloroform and chlorobenzene; ketone solvents such as acetone,methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such asmethanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butylalcohol; nitrile solvents such as acetonitrile, propionitrile andbenzonitrile; ester solvents such as ethyl acetate and butyl acetate;carbonate solvents such as ethylene carbonate and propylene carbonate;and so on. These may be used singly or two or more of them maybe used inadmixture. It is also possible to carry out the polymerization in anemulsion system or in a system in which the supercritical fluid CO₂ isused as a medium. The above polymerization can be effected within thetemperature range of 0 to 200° C., preferably within the range of roomtemperature to 150° C.

The transition metal complex to be used as the catalyst is notparticularly restricted but includes, as preferred species, complexes ofzero-valence copper, univalent copper, bivalent ruthenium, bivalent ironor bivalent nickel. Among them, copper complexes are preferred. Asspecific examples of the univalent copper compound, there may bementioned cuprous chloride, cuprous-bromide, cuprous iodide, cuprouscyanide, cuprous oxide and cuprous perchlorate. When a copper compoundis used, a ligand, for example 2,2′-bipyridyl or a derivative thereof,1,10-phenanthroline or a derivative thereof, or a polyamine such astetramethylethylenediamine, pentamethyl-diethylenetriamine orhexamethyltris(2-aminoethyl)amine, is added for increasing the catalyticactivity. The tristriphenylphosphine complex of bivalent rutheniumchloride (RuCl₂(PPh₃)₃) is also suited for use as a catalyst. When aruthenium compound is used as a catalyst, an aluminum alkoxide is addedas an activator. Further, the bistriphenylphosphine complex of bivalentiron (FeCl₂(PPh₃)₂) the bistriphenylphosphine complex of bivalent nickel(NiCl₂(PPh₃) ₂) and the bistributylphosphine complex of bivalent nickel(NiBr₂(PBu₃)₂) are also suited as catalysts.

The compound having both an ethylenically unsaturated group and areactive functional group is not particularly restricted but includes,among others, hydroxy-containing vinyl monomers such as 2-hydroxyethyl(meth)acrylate and 2-hydroxypropyl (meth)acrylate; amido-containingvinyl monomers such as (meth)acrylamide; amino-containing vinyl monomerssuch as 2-aminoethyl (meth)acrylate; carboxyl-containing vinyl monomerssuch as (meth)acrylic acid, maleic acid, maleic acid monoalkyl esters,fumaric acid and fumaric acid monoalkyl esters, and the like.

Further, maleic anhydride; maleimide monomers such as maleimide,methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide,hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide,phenylmaleimide and cyclohexylmaleimide; tert-butoxystyrene;acetoxystyrene; and the like may also be used.

Further, phenols having an ethylenically unsaturated group, such as o-,m- and p-allylphenol and o-, m- and p-allyloxyphenol; alcohols having anethylenically unsaturated group, such as allyl alcohol, butenyl alcohol,pentenyl alcohol and hexenyl alcohol; amines having an ethylenicallyunsaturated group, such as allylamine, butenylamine, pentenylamine andhexenylamine; carboxylic acid compounds having an ethylenicallyunsaturated group, such as vinyl acetate, pentenoic acid, heptenoic acidand undecenoic acid; and the like may also be used.

When the above compound having both an ethylenically unsaturated groupand a reactive functional group is reacted with the polymer terminus,the compound as such may be subjected to reaction. In some cases,however, the reactive functional group may affect the polymer terminusand, in such cases, it may be used in the form having a protectivegroup. As the protective group, there may be mentioned acetyl, silylgroups and alkoxy groups, among others. Suited for use as the compoundhaving a protective functional group are all the compounds mentionedabove whose functional group is protected.

The above compound having both a reactive functional group and anethylenically unsaturated group may be subjected to reaction with thepolymer isolated after completion of the vinyl monomer polymerization byadding to that polymer together with a catalyst or may be added andsubjected to reaction in the course of polymerization (in situ). In thelatter case, the monomer conversion of the first polymerization shouldbe as high as possible, preferably not less than 80%. If the conversionis not more than 80%, the crosslinking silyl group is distributed onside chains, not at molecular termini, whereby the mechanicalcharacteristics of cured products will be impaired. In principle, theaddition of such compound having a polymerizable alkenyl group and acrosslinking silyl group in an equivalent amount relative to the wholenumber of termini results in introduction of the functional group at alltermini. For securing the introduction of the functional group at alltermini, however, it is recommendable to use the compound in excess,specifically in an amount of 1 to 5 times excess relative to the numberof termini. When it is used in an amount not less than 5 times, thefunctional group is introduced terminally into the polymer at anexcessively high density and this is unfavorable from the cured productphysical properties viewpoint.

In the first aspect of the invention, the vinyl polymer having areactive functional group is also produced by the following steps:

(1) Producing a vinyl polymer having a terminal structure represented bythe following general formula 3 (a vinyl polymer having a halogen atomat a main chain terminus) by subjecting vinyl monomers to atom transferradical polymerization, namely radical polymerization using an organichalide or halogenated sulfonyl compound as an initiator and a transitionmetal complex as a catalyst:

—C(R⁶)(R⁷)(X)  (3)

 wherein R⁶ and R⁷ each represents a group bound to the ethylenicallyunsaturated group and X represents a chlorine, bromine or iodine atom)and

(2) Converting the halogen atom in general formula (3) to a substituenthaving a reactive functional group.

The initiators, catalysts, solvents, polymerization conditions and soforth as already mentioned hereinabove specifically for atom transferradical polymerization all can adequately be used.

As the method of converting the halogen at a polymer terminus, there maybe mentioned, for example, the nucleophilic substitution reaction usinga nucleophilic reagent having a reactive functional group. As suchnucleophilic reagent, there may be mentioned, among others, alcoholcompounds, phenol compounds, carboxylic compounds, amine compounds andamide compounds each having a reactive functional group, and alkalimetal salts or ammonium salts thereof. Carbanions having a reactivefunctional group and stabilized by an electron-attracting substituentare also suited for use. Specific examples of the nucleophilic reagentare shown below.

As the alcohols having a reactive function group, there maybe mentioned,among others, aliphatic diols such as ethylene glycol; alicyclic diolssuch as 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol,1,3-cyclohexanediol and 1,4-cyclohexanediol; amino-containing alcoholssuch as ethanolamine; and the like.

As the phenols having a reactive function group, there may be mentioned,among others, compounds having two phenolic hydroxyl groups in eachmolecule, such as hydroquinone, catechol, resorcinol, bisphenol A andbiphenol; and the like.

As the carboxylic acids having a reactive function group, there may bementioned, among others, hydroxyl-containing carboxylic acid compoundssuch as HO—(CH₂)_(n)—CO₂H (n being an integer of 0 to 10); carboxylicacid compounds having a phenolic hydroxyl group, such as hydroxybenzoicacid and 4′-hydroxy-4-biphenylcarboxylic acid; amino acid compounds;dibasic carboxylic acids such as oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, HO₂C—(CH₂)_(n)—CO₂H (n being aninteger of 5 to 20), 1,2-cyclopentanedicarboxylic acid,1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,1,4-cyclohexanedicarboxylic acid, maleic acid, fumaric acid, malic acid,tartaric acid, phthalic acid, isophthalic acid, terephthalic acid andnaphthalenedicarboxylic acids; halides of the dibasic carboxylic acidsmentioned above; cyclic acid anhydrides such as succinic anhydride,maleic anhydride and phthalic anhydride; and the like.

As the amines having a reactive function group, there may be mentioned,among others, hydroxyl-containing amines such as ethanolamine; diaminecompounds such as ethylenediamine, 1,3-diaminopropane,1,2-diaminopropane, 1,4-diaminobutane, 1,2-diamino-2-methylpropane,1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,6-hexanediamine,1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine,1,10-decanediamine, 1,12-dodecanediamine,4,4′-methylenebis(cyclohexylamine), 1,2-diaminocyclohexane,1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-phenylenediamine,1,3-phenylenediamine, 1,4-phenylenediamine and α,α′-diamino-p-xylene;and the like.

Alkali metal salts and ammonium salts of the above-mentioned variousnucleophilic reagents may also be used as nucleophilic reagents. Thealkali metal salts and ammonium salts are obtained by reacting the abovenucleophilic reagents with a basic compound. The basic compound is notparticularly restricted but, for preparing alkali metal salts, forinstance, use is made of alkali metals such as potassium, sodium andlithium; metal alkoxides such as sodium methoxide, potassium methoxide,lithium methoxide, sodium ethoxide, potassium ethoxide, lithiumethoxide, sodium tert-butoxide and potassium tert-butoxide; carbonatessuch as sodium carbonate, potassium carbonate, lithium carbonate andsodium hydrogen carbonate; hydroxides such as sodium hydroxide andpotassium hydroxide; hydrides such as sodium hydride and potassiumhydride; organolithium compounds such as methyllithium, ethyllithium,n-butyllithium, tert-butyllithium, lithium diisopropylamide and lithiumhexamethyldisilazide; and like bases. In preparing ammonium salts, useis made of, for example, ammonium, amines such as trimethylamine,triethylamine, tributylamine, tetramethylethylenediamine and pentamethyldiethylenetriamine; pyridine compounds such as pyridine and picoline;and like nitrogen bases.

Quaternary ammonium salts may also be used as the nucleophilic reagent.The quaternary ammonium salts can be prepared by reacting the alkalimetal salts mentioned above with a quaternary ammonium halide. Thequaternary ammonium halide is not particularly restricted but includes,among others, tetramethylammonium halides, tetraethylammonium halides,trimethylbenzylammonium halides, trimethyldodecylammonium halides andtetrabutylammonium halides.

As the solvent to be used in the nucleophilic substitution reaction,there may be mentioned, among others, hydrocarbon solvents such asbenzene, toluene and xylene; halogenated hydrocarbon solvents such asmethylene chloride, chloroform and chlorobenzene; ether solvents such asdiethyl ether, dioxane, tetrahydrofuran, diphenyl ether, anisole anddimethoxybenzene; ester solvents such as ethyl acetate and butylacetate; ketone solvents such as acetone, methyl ethyl ketone and methylisobutyl ketone; alcohol solvents such as methanol, ethanol, propanol,isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solventssuch as acetonitrile, propionitrile and benzonitrile; amide solventssuch as dimethylformamide, dimethylacetamide and hexamethylphosphorictriamide; sulfoxide solvents such as dimethyl sulfoxide; carbonatesolvents such as ethylene carbonate and propylene carbonate; water andso on. These may be used singly or two or more of them may be used inadmixture. The substitution reaction can be carried out at 0 to 150° C.

For promoting the substitution reaction, a basic compound may be addedto the reaction system. All the bases already specifically mentionedhereinabove may adequately be used as the base.

A phase transfer catalyst such as a quaternary ammonium halide and crownether may also be added to the reaction system for promoting thesubstitution reaction. Those already specifically mentioned hereinabovemay be used as the quaternary ammonium halide.

As already mentioned hereinabove, a vinyl polymer having a functionalgroup at both termini can be produced also by polymerizing vinylmonomers using an initiator having a reactive functional group, followedby coupling of a polymer terminus with another. As the method ofcoupling, there may be mentioned, for example, a method which comprisescoupling terminal halogens with each other using a compound having atotal of two or more functional groups which may be the same ordifferent and each can substitute the terminal halogen in the generalformula 3.

The compound having a total of two or more functional groups eachcapable of substituting the terminal halogen atom is not particularlyrestricted but preferably is a polyol, polyamine, polycarboxylic acid orpolythiol, or a salt thereof, an alkali metal sulfide or the like.Specific examples of these compounds are as follows:

Polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol,2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol,1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol,1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,6-hexanediol,1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1, 10-decanediol,1,12-dodecanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol,1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, glycerol,1,2,4-butanetriol, catechol, resorcinol, hydroquinone,1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene,1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,2′-biphenol,4,4′-biphenol, bis(4-hydroxyphenyl)methane, 4,4′-isopropylidenephenol,3,3′-(ethylenedioxy)diphenol, α,α′-dihydroxy-p-xylene,1,1,1-tris(4-hydroxyphenyl)ethane, pyrogallol and 1,2,4-benzenetriol;and alkali metal salts of the above polyol compounds;

Polyamines such as ethylenediamine, 1,3-diaminopropane,1,2-diaminopropane, 1,4-diaminobutane, 1,2-diamino-2-methylpropane,1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,6-hexanediamine,1,7-heptanediamine, 1,8-octanediamine, 1,9-diaminononane,1,10-diaminodecane, 1,12-diaminododecane,4,4′-methylenebis(cyclohexylamine), 1,2-diaminocyclohexane,1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-phenylenediamine,1,3-phenylenediamine, 1,4-phenylenediamine and α,α′-diamino-p-xylene;and alkali metal salts of the above polyamines;

Polycarboxylic acids such as oxalic acid, malonic acid, methylmalonicacid, dimethylmalonic acid, succinic acid, methylsuccinic acid, glutaricacid, adipic acid, 1,7-heptanedicarboxylic acid, 1,8-octanedicarboxylicacid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid,1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid,1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid,1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,1,3,5-cyclohexanetricarboxylic acid, phthalic acid, isophthalic acid,terephthalic acid, 1,2,3-benzenetricarboxylic acid and1,2,4,5-benzenetetracarboxylic acid; and alkali metal salts of the abovepolycarboxylic acids;

Polythiols such as 1,2-ethanedithiol, 1,3-propanedithiol,1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol,1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol,1,9-nonanedithiol, 2-mercaptoethyl ether, p-xylene-α,α′-dithiol,1,2-benzenedithiol, 1,3-benzenedithiol and 1,4-benzenedithiol; andalkali metal salts of the above polythiol compounds;

Lithium sulfide, sodium sulfide and potassium sulfide; and so forth.

For promoting the substitution reaction, a basic compound or aquaternary ammonium salt may also be added. As specific examplesthereof, those already specifically mentioned hereinabove may bementioned.

The vinyl polymer having a reactive functional group at a main chainterminus according to the first aspect of the invention can also beproduced by radical polymerization of a vinyl monomer(s) using a chaintransfer agent having a reactive function group(s).

The reactive functional group-terminated vinyl polymer obtained in theabove manner, when reacted with a compound represented by the generalformula (2), gives a vinyl polymer terminally having a group representedby the general formula (1). The reactive functional group-terminatedvinyl polymer is produced by the method already mentioned.

The compound represented by the general formula (2) is not particularlyrestricted but epichlorohydrin and epibromohydrin are preferred becauseof ready availability.

As the solvent to be used in carrying out the reaction, there may bementioned, among others, hydrocarbon solvents such as benzene, tolueneand xylene; halogenated hydrocarbon solvents such as methylene chloride,chloroform and chlorobenzene; ether solvents such as diethyl ether,dioxane, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene;ester solvents such as ethyl acetate and butyl acetate; ketone solventssuch as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcoholsolvents such as methanol, ethanol, propanol, isopropanol, n-butylalcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile,propionitrile and benzonitrile; amide solvents such asdimethylformamide, dimethylacetamide and hexamethylphosphoric triamide;sulfoxide solvents such as dimethyl sulfoxide; carbonate solvents suchas ethylene carbonate and propylene carbonate; water and so on. Thesemay be used singly or two or more of them may be used in admixture.

The reaction is desirably carried out in the presence of a basiccompound. As such basic compound, all specifically mentioned hereinabovecan adequately be used. For accelerating the reaction, any of the phasetransfer catalysts known in the art may be added to the reaction system.As examples of the phase transfer catalyst, there may be mentionedquaternary ammonium salts and crown ethers, among others.

The vinyl polymer having a group represented by the general formula (1)as produced according to the invention can be made into an epoxy resincomposition and this constitutes one aspect of the invention.

This composition generally comprises the following two components: thevinyl polymer having a group represented by the general formula (1) at amain chain terminus and an epoxy resin curing agent.

The vinyl polymer may comprise a single species or a mixture of two ormore species.

The epoxy resin curing agent is not particularly restricted but use maybe made of such photo- or ultraviolet-curing agents as aliphatic amines,alicyclic amines, aromatic amines; acid anhydrides; polyamides;imidazoles; amineimides; urea; melamine and derivatives thereof;polyamine salts; phenol resins; polymercaptans, polysulfides; aromaticdiazonium salts; diallyliodonium salts, triallylsulfonium salts,triallylselenium salts and the like .

Further, an epoxy resin known in the art may be used in combination withthe vinyl polymer of the invention. Such epoxy resin is not particularlyrestricted but includes, but is not limited to, glycidyl ether typeepoxy resins derived from bisphenol A, bisphenol F ortetrabromobisphenol A, novolak type epoxy resins, hydrogenated bisphenolA-based epoxy resins, glycidyl ether type epoxy resins derived frombisphenol A-propylene oxide adducts, p-hydroxybenzoic acid glycidylether ester type epoxy resins, m-aminophenol-based epoxy resins,diaminodiphenylmethane-based epoxy resins, urethane-modified epoxyresins, various alicyclic epoxy resins, N,N-diglycidylaniline,N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkyleneglycol diglycidyl ethers, glycidyl ethers of polyhydric alcohols such asglycerol, hydantoin type epoxy resins, epoxidization products fromunsaturated polymers such as petroleum resins and the like. These epoxyresins may be used singly or two or more of them may be used inadmixture.

For improving the mechanical/physical properties or cured products,various fillers may be incorporated. Usable as the fillers arereinforcing fillers such as fumed silica, precipitated silica, silicicanhydride, hydrous silicic acid and carbon black; such fillers ascalcium carbonate, magnesium carbonate, diatomaceous earth, calcinedclay, clay, talc, titanium oxide, bentonite, organic bentonite, ferricoxide, zinc oxide, activated zinc white and sirasu balloons; and fibrousfillers such as asbestos, and glass fibers and filaments. For obtainingcured products having high strength using these fillers, a fillerselected mainly from among fumed silica, precipitated silica, silicicanhydride, hydrous silicic acid, carbon black, surface-treated, finelydivided calcium carbonate, calcined clay, clay, activated zinc white andthe like is used in an amount within the range of 1 to 100 parts byweight per 100 parts by weight of the (meth)acrylic polymer, whereuponfavorable results can be obtained. For obtaining cured products low instrength but high in elongation, a filler selected mainly from amongtitanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide andsirasu balloons is used in an amount within the range of 5 to 200 partsby weight per 100 parts of the (meth)acrylic polymer to give favorableresults. These fillers may be used singly or two or more of them may beused in admixture.

It is also possible to use various plasticizers, coupling agents, moldrelease agents and so forth.

Now, the second aspect of the invention is explained.

The second aspect of the invention lies in an epoxy resin compositioncomprising two components, namely (A) an epoxy resin and (B) a vinylpolymer having a main chain produced by living radical polymerizationand a reactive functional group at a main chain terminus.

The component (A) epoxy resin according to the second aspect of theinvention is not particularly restricted but includes various ones.Examples include, but are not limited to glycidyl ether type epoxyresins derived from bisphenol A, bisphenol F, tetrabromobisphenol A orthe like, novolak type epoxy resins, hydrogenated bisphenol A-basedepoxy resins, glycidyl ether type epoxy resins derived from bisphenolA-propylene oxide adducts, p-hydroxybenzoic acid glycidyl ether estertype epoxy resins, m-aminophenol-based epoxy resins,diaminodiphenylmethane-based epoxy resins, urethane-modified epoxyresins, various alicyclic epoxy resins, N,N-diglycidylaniline,N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkyleneglycol diglycidyl ethers, glycidyl ethers of polyhydric alcohols such asglycerol, hydantoin type epoxy resins, epoxidation products derived fromunsaturated polymers such as petroleum resins, and the like. These epoxyresins may be used singly or two or more of them may be used inadmixture.

The reactive functional group according to the second aspect of theinvention is not particularly restricted but may be any functional groupcapable of reacting with the epoxy group of the epoxy resin to therebyeffect crosslinking. As examples, there may be mentioned an alcoholichydroxyl group, a phenolic hydroxyl group, an amino group, an amidegroup and a carboxyl group.

The vinyl type monomer constituting the main chain of the vinyl polymerin the second aspect of the invention is not particularly restricted butmay be any of those mentioned hereinabove referring to the first aspectof the invention.

The molecular weight distribution of the above vinyl polymer is notparticularly restricted but, generally, the ratio (Mw/Mn) of weightaverage molecular weight (Mw) to number average molecular weight (Mn) asdetermined by gel permeation chromatography is less than 1.8, preferablynot more than 1.7, more preferably not more than 1.6, still morepreferably not more than 1.5, especially preferably not more than 1.4,most preferably not more than 1.3. In the practice of the invention, GPCmeasurements are generally carried out using polystyrene gel columnswith chloroform as the mobile phase and the number average molecularweight and so on can be determined on the polystyrene equivalent basis.

The number average molecular weight of the vinyl polymer in the practiceof the second aspect of the invention is not particularly restricted butpreferably is within the range of 500 to 1,000,000, more preferably1,000 to 100,000.

The vinyl polymer having a reactive functional group which is to be usedin the practice of the second aspect of the invention may be any polymerterminally having a reactive functional group. In view of the ease ofcontrol of the molecular weight, molecular weight distribution and ofterminal functional group introduction, however, the above-mentionedliving radical polymerization method is preferably employed as themethod of producing the main chain of the vinyl polymer.

For producing the vinyl polymer having a reactive functional group byusing the living radical polymerization, a process comprising thefollowing steps, for instance, may be mentioned:

(1) Forming a vinyl polymer by polymerizing a vinyl monomer(s) by theliving radical polymerization technique and

(2) Reacting, at the end point of the polymerization, the polymer with acompound having both a reactive functional group and an ethylenicallyunsaturated group.

The compound having both an ethylenically unsaturated group and areactive functional group is not particularly restricted but includes,among others, hydroxy-containing vinyl monomers such as 2-hydroxyethyl(meth)acrylate and 2-hydroxypropyl (meth)acrylate; amido-containingvinyl monomers such as (meth)acrylamide; amino-containing vinyl monomerssuch as 2-aminoethyl (meth)acrylate; carboxyl-containing vinyl monomerssuch as (meth)acrylic acid, maleic acid, maleic acid monoalkyl esters,fumaric acid and fumaric acid monoalkyl esters, and the like.

Further, maleic anhydride; maleimide monomers such as maleimide,methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide,hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide,phenylmaleimide and cyclohexylmaleimide; tert-butoxystyrene;acetoxystyrene; and the like may also be used.

Further, phenols having an ethylenically unsaturated group, such as o-,m- and p-allylphenol and o-, m- and p-allyloxyphenol; alcohols having anethylenically unsaturated group, such as allyl alcohol, butenyl alcohol,pentenyl alcohol and hexenyl alcohol; amines having an ethylenicallyunsaturated group, such as allylamine, butenylamine, pentenylamine andhexenylamine; carboxylic acid compounds having an ethylenicallyunsaturated group, such as vinyl acetate, pentenoic acid, heptenoic acidand undecenoic acid; and the like may also be used.

When the compound having both an ethylenically unsaturated group and areactive functional group is reacted with the polymer terminus, thecompound as such may be subjected to reaction. In some cases, however,the reactive functional group may affect the polymer terminus and, insuch cases, it may be used in the form having a protective group. As theprotective group, there may be mentioned acetyl, silyl groups and alkoxygroups, among others. Suited for use as the compound having a protectivegroup are all the compounds mentioned above whose functional group isprotected.

The compound having both a reactive functional group and anethylenically unsaturated group may be subjected to reaction with thepolymer isolated after completion of the vinyl monomer polymerization bynewly adding that compound to that polymer together with a catalyst ormay be added and subjected to reaction in the course of polymerization(in situ). In the latter case, the monomer conversion of the firstpolymerization should be as high as possible, preferably not less than80%. If the conversion is not more than 80%, the reactive functionalgroup is distributed on side chains, not at molecular termini, wherebythe mechanical characteristics of cured products will be impaired. Inprinciple, the addition of such compound having a reactive functionalgroup and an ethylenically unsaturated group in an equivalent amountrelative to the whole number of termini results in introduction of thefunctional group at all termini. For securing the introduction of thefunctional group at all termini, however, it is recommendable to use thecompound in excess, specifically in an amount of 1 to 5 times excessrelative to the number of termini. When it is used in an amount not lessthan 5 times, the functional group is introduced terminally into thepolymer at an excessively high density and this is unfavorable from thecured product physical properties viewpoint.

The vinyl polymer having a reactive functional group according to theinvention may also be produced by the following steps:

(1) Producing a vinyl polymer terminally having a halogen, and

(2) Converting the halogen at the polymer terminus to a substituenthaving a reactive functional group.

A chlorine, bromine or iodine atom is preferred as the halogen. As themethod of producing the halogen-terminated vinyl polymer, there may bementioned the radical polymerization method using a halide compound as achain transfer agent and the above-mentioned atom transfer radicalpolymerization. In view of the ease of control of the molecular weightand molecular weight distribution, the latter is preferred. Theinitiators, catalysts, solvents, polymerization conditions and so forthas already mentioned hereinabove specifically for atom transfer radicalpolymerization all can adequately be used.

As the method of converting the halogen at a polymer terminus, there maybe mentioned, for example, the nucleophilic substitution reaction usinga nucleophilic reagent having a reactive functional group. As suchnucleophilic reagent, there may be mentioned, among others, alcohols,phenols, carboxylic acids and amines each having a reactive functionalgroup, and alkali metal salts or ammonium salts thereof. Carbanionshaving a reactive functional group and stabilized by anelectron-attracting substituent are also suited for use. Specificexamples of the nucleophilic reagent are shown below.

As the alcohols having a reactive function group, there may bementioned, among others, aliphatic diols such as ethylene glycol;alicyclic diols such as 1,2-cyclopentanediol, 1,3-cyclopentanediol,1,2-cyclohexanediol, 1,3-cyclohexanediol and 1,4-cyclohexanediol;amino-containing alcohols such as ethanolamine; and the like.

As the phenols having a reactive function group, there may be mentioned,among others, compounds having two phenolic hydroxyl groups in eachmolecule, such as hydroquinone, catechol, resorcinol, bisphenol A andbiphenol; and the like.

As the carboxylic acids having a reactive function group, there may bementioned, among others, hydroxyl-containing carboxylic acid compoundssuch as HO—(CH₂)_(n)—CO₂H (n being an integer of 0 to 10); carboxylicacid compounds having a phenolic hydroxyl group, such as hydroxybenzoicacid and 4′-hydroxy-4-biphenylcarboxylic acid; amino acid compounds;dibasic carboxylic acids such as oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, HO₂C—(CH₂)_(n)—CO₂H (n being aninteger of 5 to 20), 1,2-cyclopentanedicarboxylic acid,1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,1,4-cyclohexanedicarboxylic acid, maleic acid, fumaric acid, malic acid,tartaric acid, phthalic acid, isophthalic acid, terephthalic acid andnaphthalenedicarboxylic acids; halides of the dibasic carboxylic acidsmentioned above; cyclic acid anhydrides such as succinic anhydride,maleic anhydride and phthalic anhydride; and the like.

As the amines having a reactive function group, there may be mentioned,among others, aliphatic amines, alicyclic amines and aromatic amineseach having a reactive functional group.

Alkali metal salts and ammonium salts of the above-mentioned variousnucleophilic reagents may also be used as nucleophilic reagents. Thealkali metal salts and ammonium salts are obtained by reacting the abovenucleophilic reagents with a basic compound. The basic compound is notparticularly restricted but includes, among others, alkali metals suchas potassium, sodium and lithium; metal alkoxides such as sodiummethoxide, potassium methoxide, lithium methoxide, sodium ethoxide,potassium ethoxide, lithium ethoxide, sodium tert-butoxide and potassiumtert-butoxide; carbonates such as sodium carbonate, potassium carbonate,lithium carbonate and sodium hydrogen carbonate; hydroxides such assodium hydroxide and potassium hydroxide; hydrides such as sodiumhydride and potassium hydride; organolithium compounds such asmethyllithium, ethyllithium, n-butyllithium, tert-butyllithium, lithiumdiisopropylamide and lithium hexamethyldisilazide; ammonium, amines suchas trimethylamine, triethylamine, tributylamine,tetramethylethylenediamine and pentamethyldiethylenetriamine; pyridinecompounds such as pyridine and picoline; and the like.

Quaternary ammonium salts may also be used as the nucleophilic reagent.The quaternary ammonium salts can be prepared by reacting the alkalimetal salts mentioned above with a quaternary ammonium halide. Thequaternary ammonium halide is not particularly restricted but includes,among others, tetramethylammonium halides, tetraethylammonium halides,trimethylbenzylammonium halides, trimethyldodecylammonium halides andtetrabutylammonium halides.

As the solvent to be used in the nucleophilic substitution reaction,there may be mentioned, among others, hydrocarbon solvents such asbenzene, toluene and xylene; halogenated hydrocarbon solvents such asmethylene chloride, chloroform and chlorobenzene; ether solvents such asdiethyl ether, dioxane, tetrahydrofuran, diphenyl ether, anisole anddimethoxybenzene; ester solvents such as ethyl acetate and butylacetate; ketone solvents such as acetone, methyl ethyl ketone and methylisobutyl ketone; alcohol solvents such as methanol, ethanol, propanol,isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solventssuch as acetonitrile, propionitrile and benzonitrile; amide solventssuch as dimethylformamide, dimethylacetamide and hexamethylphosphorictriamide; sulfoxide solvents such as dimethyl sulfoxide; carbonatesolvents such as ethylene carbonate and propylene carbonate; water andso on. These may be used singly or two or more of them may be used inadmixture. The substitution reaction can be carried out at 0 to 150° C.

For promoting the substitution reaction, a basic compound may be addedto the reaction system. All the bases already specifically mentionedhereinabove may adequately be. used as the base.

A phase transfer catalyst such as a quaternary ammonium halide and crownether may also be added to the reaction system for promoting thesubstitution reaction.

As already mentioned hereinabove, a vinyl polymer having a functionalgroup at both termini Can be produced also by polymerizing vinylmonomers using an initiator having a reactive functional group, followedby coupling of a polymer terminus with another. As the method ofcoupling, there may be mentioned, for example, a method which comprisescoupling terminal halogens with each other using a compound having atotal of two or more functional groups which may be the same ordifferent and each can substitute the polymer terminal halogen.

The compound having a total of two or more functional groups which maybe the same or different and each can substitute the polymer terminalhalogen is not particularly restricted but preferably is a polyol,polyamine, polycarboxylic acid or polythiol, or a salt thereof, analkali metal sulfide or the like. Specific examples of these compoundsare as follows:

Polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol,2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol,1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol,1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,6-hexanediol,1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,1,12-dodecanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol,1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, glycerol,1,2,4-butanetriol, catechol, resorcinol, hydroquinone,1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene,1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,2′-biphenol,4,4,′-biphenol, bis(4-hydroxyphenyl)methane, 4,4′-isopropylidenephenol,3,3′-(ethylenedioxy)diphenol, α,α′-dihydroxy-p-xylene,1,1,1-tris(4-hydroxyphenyl)ethane, pyrogallol and 1,2,4-benzenetriol;and alkali metal salts of the above polyol compounds;

Polyamines such as ethylenediamine, 1,3-diaminopropane,1,2-diaminopropane, 1,4-diaminobutane, 1,2-diamino-2-methylpropane,1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,6-hexanediamine,1,7-heptanediamine, 1,8-octanediamine, 1,9-diaminononane,1,10-diaminodecane, 1,12-diaminododecane,4,4′-methylenebis(cyclohexylamine), 1,2-diaminocyclohexane,1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-phenylenediamine,1,3-phenylenediamine, 1,4-phenylenediamine and α,α′-diamino-p-xylene;and alkali metal salts of the above polyamines;

Polycarboxylic acids such as oxalic acid, malonic acid, methylmalonicacid, dimethylmalonic acid, succinic acid, methylsuccinic acid, glutaricacid, adipic acid, 1,7-heptanedicarboxylic acid, 1,8-octanedicarboxylicacid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid,1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid,1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid,1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,1,3,5-cyclohexanetricarboxylic acid, phthalic acid, isophthalic acid,terephthalic acid, 1,2,3-benzenetricarboxylic acid and1,2,4,5-benzenetetracarboxylic acid; and alkali metal salts of the abovepolycarboxilic acids;

Polythiols such as 1,2-ethanedithiol, 1,3-propanedithiol,1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol,1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol,1,9-nonanedithiol, 2-mercaptoethyl ether, p-xylene-α,α′-dithiol,1,2-benzenedithiol, 1,3-benzenedithiol and 1,4-benzenedithiol; andalkali metal salts of the above polythiol compounds;

Lithium sulfide, sodium sulfide and potassium sulfide; and so forth.

For promoting the reaction, a basic compound may also be added to thereaction system. As the base to be used, those already specificallymentioned hereinabove all are suited for use.

For promoting the reaction, a phase transfer catalyst such as aquaternary ammonium halide and crown ether may also be added to thereaction system.

The epoxy resin composition according to the second aspect of theinvention comprises, as essential components, the epoxy resin, namelythe above-mentioned (A) component, and the vinyl polymer terminallyhaving a reactive functional group, namely the above-mentioned (B)component. The mixing ratio between the both components is generallysuch that the vinyl polymer accounts for 0.1 to 1,000 parts by weight,preferably 1 to 500 parts by weight, more preferably 1 to 200 parts byweight, per 100 parts by weight of the epoxy resin. At an additionamount below 0.1 part by weight, the effects of incorporation are notfully produced. At an amount above 1,000 parts by weight, the rate ofcuring unfavorably falls.

The invention also includes the combined use of an epoxy resin curingagent known in the art. As examples of such curing agent, there may bementioned:

Primary amines such as diethylenetriamine, triethylenetetramine,tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine,N-aminoethylpiperazine, BASF's Lamilon C-260, CIBA's Araldite HY-964,Rohm and Haas' Menthenediamine, isophoronediamine,diaminodicyclohexylmethane, m-xylylenediamine, m-phenylenediamine,diaminodiphenylmethane and diaminodiphenyl sulfone, straight-chaindiamines represented by (CH₃)₂N(CH₂)_(n)N(CH₃)₂ (n being an integer of 1to 10), straight-chain tertiary amines represented by(CH₃)₂N(CH₂)_(n)CH₃ (n being an integer of 0 to 10),tetramethylguanidine, alkyl-tertiary monoamines represented byN[(CH₂)_(n)CH₃]₃ (n being an integer of 1 to 10), triethanolamine,piperidine, N,N′-dimethylpiperazine, triethylenediamine, pyridine,picoline, diazabicycloundecene, benzyldimethylamine,2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol andlike secondary or tertiary amines, acid anhydrides such as phthalicanhydride, trimellitic anhydride and benzophenonetetracarboxylicanhydride, various polyamide resins, dicyandiamide and derivativesthereof, various imidazoles, and the like.

For improving the mechanical/physical properties of cured products,various fillers may be incorporated. Usable as the fillers arereinforcing fillers such as fumed silica, precipitated silica, silicicanhydride, hydrous silicic acid and carbon black; such fillers ascalcium carbonate, magnesium carbonate, diatomaceous earth, calcinedclay, clay, talc, titanium oxide, bentonite, organic bentonite, ferricoxide, zinc oxide, activated zinc white and sirasu balloons; and fibrousfillers such as asbestos, and glass fibers and filaments. For obtainingcured products having high strength using these fillers, a fillerselected mainly from among fumed silica, precipitated silica, silicicanhydride, hydrous silicic acid, carbon black, surface-treated, finelydivided calcium carbonate, calcined clay, clay, activated zinc white andthe like is used in an amount within the range of 1 to 100 parts byweight per 100 parts by weight of the (meth)acrylic polymer, whereuponfavorable results can be obtained. For obtaining cured products low instrength but high in elongation, a filler selected mainly from amongtitanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide andsirasu balloons is used in an amount within the range of 5 to 200 partsby weight per 100 parts of the (meth)acrylic polymer to give favorableresults. These fillers may be used singly or two or more of them may beused in admixture.

It is also possible to use various plasticizers, coupling agents, moldrelease agents and so forth.

As specific uses of the composition of the present invention, there maybe mentioned, among others, sealing materials, adhesives, pressuresensitive adhesives, elastic adhesives, coating compositions, powdercoating compositions, foamed or expanded articles, potting agents forelectric and electronic use, films, molding materials and artificialmarble.

BEST MODES FOR CARRYING OUT THE INVENTION

In the following, some specific examples of the present invention aredescribed together with a comparative example. They are, however, by nomeans limitative of the scope of the invention. In the examples, the“number average molecular weight” and “molecular weight distribution(ratio between weight average molecular weight and number averagemolecular weight)” were determined by the standard polystyreneequivalent method using gel permeation chromatography (GPC). Columnspacked with crosslinked polystyrene gels were used as GPC columns andchloroform was used as the GPC solvent.

PRODUCTION EXAMPLE 1 Synthesis of Br-terminated poly(butyl acrylate)

A 10-liter separable flask equipped with a reflux condenser and astirrer was charged with CuBr (28.0 g, 0.20 mol) and the reactor insidewas purged with nitrogen. Acetonitrile (559 mL) was added, and thecontents were stirred on an oil bath at 70° C. for 40 minutes. Theretowere added butyl acrylate (1.00 kg), diethyl 2,5-dibromoadipate (117 g,0.325 mol) and pentamethyldiethylenetriamine (hereinafter, “triamine”;1.7 mL, 1.4 g, 8.1 mmol) to thereby start the reaction. While heating at70° C. with stirring, butyl acrylate (4.00 kg) was added dropwisecontinuously. During dropping of butyl acrylate, the triamine (8.5 mL,7.06 g, 0.041 mol) was further added.

The reaction mixture was diluted with toluene and passed through anactivated alumina column, and the volatile matter was then distilled offunder reduced pressure to give a Br-terminated polymer (polymer [1]).The polymer [1] had a number average molecular weight of 19,500 and amolecular weight distribution of 1.17.

EXAMPLE 1 Synthesis of a phenol group-terminated poly(butyl acrylate)

A 100-ml reaction vessel was charged with the polymer [1] (50 g)obtained in Production Example 1, potassium p-hydroxybenzoate (1.96 g,11.1 mmol) and dimethylacetamide (50 mL). The contents were heated at70° C. with stirring for 3 hours under a stream of nitrogen. Thereaction mixture was diluted with toluene and passed through anactivated alumina column, and the volatile matter was then distilled offunder reduced pressure. The polymer obtained was dissolved in tolueneand the solution was again passed through an activated alumina column,and the toluene was distilled off under reduced pressure to givephenol-terminated poly(butyl acrylate) (polymer [2]). The average numberof phenol groups introduced per molecule of the polymer was determinedto be 2.3 by ¹H NMR spectrometry.

EXAMPLE 2 Synthesis of an epoxy-terminated poly(butyl acrylate)

A 50-mL two-necked flask equipped with a reflux condenser was chargedwith the polymer [2] (5.0 g) obtained in Production Example 2,tert-butoxypotassium (0.070 mg) and dimethylacetamide (10 mL), and thecontents were heated at 70° C. with stirring. Epichlorohydrin (2.5 mL)was added, and the mixture was heated at 70° C. with stirring for 1hour. The reaction mixture was diluted with toluene and passed throughan activated alumina column, and the volatile matter was then distilledoff under reduced pressure. The polymer obtained was dissolved intoluene and the solution was again passed through an activated aluminacolumn, and the toluene was distilled off under reduced pressure to givea polymer [3].

Upon analysis of the polymer [3] by ¹H NMR spectrometry, an epoxygroup-due peak was observed at around 2.9 ppm, indicating that the epoxygroup introduction into the polymer had been accomplished.

EXAMPLE 3 Modification of an epoxy resin

A bisphenol A-based liquid epoxy resin (2.0 g; Epikote 825, product ofYuka Shell Epoxy Kabushiki Kaisha), the polymer [2] (2.0 g) obtained inExample 1 and a tertiary amine (0.080 g; Epicure 3010, product of YukaShell Epoxy Kabushiki Kaisha) were thoroughly mixed up and the mixturewas heated at 150° C. for 1 hour to give a cured product. The curedproduct had flexibility. The uncured fraction of the cured product wasextracted with toluene and the gel fraction of the cured product wasdetermined based on the weight ratio between the weight of the curedproduct before extraction and that after extraction and found to be 91%.

INDUSTRIAL APPLICABILITY

The terminally reactive vinyl polymer and epoxy resin composition of theinvention can improve the hard and brittle characteristics of epoxyresins and provide them flexibility, without impairing the favorablecharacteristics of the epoxy resins, such as the bond properties.

What is claimed is:
 1. An epoxy resin composition which comprises (A) anepoxy resin and (B) a vinyl polymer having a main chain produced byliving radical polymerization and a reactive functional group selectedfrom the group consisting of a phenolic hydroxyl, an amino group and anamide group at a main chain terminus, and wherein said vinyl polymer (B)is obtained by (1) producing a vinyl polymer having a halogen atom at amain chain terminus thereof by atom transfer radical polymerization and(2) converting said halogen atom to a substituent having a phenolichydroxyl, an amino group or an amide group.
 2. The epoxy resincomposition according to claim 1, wherein a main chain of the vinylpolymer (B) is obtained by polymerization of a (meth)acrylic monomer. 3.The epoxy resin composition according to claim 2, wherein the(meth)acrylic monomer is a (meth)acrylic acid ester monomer.
 4. Theepoxy resin composition according to claim 3, wherein the (meth)acrylicacid ester monomer is an acrylic acid ester monomer.
 5. The epoxy resincomposition according to claim 1, wherein a main chain of the vinylpolymer (B) is obtained by polymerization of a styrenic monomer.
 6. Theepoxy resin composition according to claim 1, wherein the vinyl polymer(B) has a ratio (Mw/Mn) between weight average molecular weight (Mw) andnumber average molecular weight (Mn) of less than 1.8 as determined bygel permeation chromatography.
 7. The epoxy resin composition accordingto claim 1, wherein the vinyl polymer (B) has a number average molecularweight within the range of 1,000 to 100,000.
 8. An epoxy resincomposition which comprises (a) an epoxy resin and (B) a vinyl polymerhaving a main chain produced by living radical polymerization and analcoholic hydroxyl or carboxyl group at a main chain terminus, said (B)vinyl polymer having a number average molecular weight of 1,000 to100,000 and a ratio (Mw/Mn) of weight average molecular weight (Mw) tonumber average molecular weight (Mn) of not more than 1.6 as determinedby gel permeation chromatography, and said (B) component accounting for1 to 500 parts by weight per 100 parts by weight of said (A) component;and wherein vinyl polymer (B) is obtained by (1) producing a vinylpolymer having a halogen atom at a main chain terminus thereof by atomtransfer radical polymerization, and (2) converting said halogen atom toa substituent having an alcoholic hydroxyl or carboxyl group.
 9. Theepoxy resin composition according to claim 1, wherein a main chain ofthe vinyl polymer (B) is obtained by polymerization of a (meth)acrylicmonomer.
 10. The epoxy resin composition according to claim 9, whereinthe (meth)acrylic monomer is a (meth)acrylic acid ester monomer.
 11. Theepoxy resin composition according to claim 10, wherein the (meth)acrylicacid ester monomer is an acrylic acid ester monomer.
 12. The epoxy resincomposition according to claim 8, wherein a main chain of the vinylpolymer (B) is obtained by polymerization of a styrenic monomer.